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The redox aqueous polymerization of acrylonitrile under pressure
Author(s) -
Mohanty Baijayantimala,
Palit Sunanda K.,
Biswas Mukul
Publication year - 1986
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1986.070320110
Subject(s) - acrylonitrile , polymerization , monomer , aqueous solution , polymer chemistry , chemistry , polymer , kinetic chain length , diffusion , radical polymerization , phase (matter) , reaction rate , thermodynamics , organic chemistry , copolymer , catalysis , physics
Effect of pressure (atmospheric to 20 X 10 6 Pa) on the K 2 S 2 O 8 –Na 2 S 2 O 4 initiated aqueous polymerization of acrylonitrile has been studied at 25°C. The conversion and rate of the polymerization tend to rise initially with increase of pressure and fall subsequently to a limiting value. The initial rise in the rate is consistent with an increase of k p or a decrease in k t due to high pressure. The ultimate tendency of the rate to fall is possibly due to a decrease in the diffusion rate of the monomer from the aqueous phase to the growing polymer radical site. The molecular weight shows a more or less similar trend except that the fall in the molecular weight begins at a lower pressure range than the same in the rate or conversion. This is explained on the basis of enhanced monomer transfer reaction. These observed kinetic characteristics are not sensitive to the appearance of heterogeneity in the system due to insoluble polymer phase in as much as homogeneous reaction systems in DMF or DMSO essentially exhibit the same features. The rate is proportional to the square root of the product of [K 2 S 2 O 8 ] and [Na 2 S 2 O 4 ] and varies linearly as the first power of the monomer concentration.